Fluorocompound having highly fluorinated norbornane structure, fluoropolymer, and their production processes

ABSTRACT

To provide a novel polymerizable fluorocompound having a highly fluorinated norbornane structure, and a polymer obtained from the compound. Further, their production processes and a novel intermediate useful for the processes. 
     A novel compound ( 1 ) such as a compound ( 11 ) or a compound ( 12 ), and its polymer. A compound ( 2 ) such as a compound ( 21 ) or ( 22 ), and a compound ( 3 ) such as a compound ( 31 ) or ( 32   M ), which are useful as an intermediate for the production of the compound ( 1 ), and its production process. However, each of Z A  to Z E  represents such as —CH(—OC(O)C(CH 3 )═CH 2 )— or —CF 2 , Each of W A  and W B  represents such as F, each of Y A  to Y E  represents such as —CH(—OH)— or —CF(CH 2 OH), and each of X A  to X E  represents such as —C(O)— or —CF 2 —.

TECHNICAL FIELD

The present invention relates to a novel compound having a highlyfluorinated norbornane structure, a fluoropolymer obtained from thecompound, and their production processes.

BACKGROUND ART

A polymerizable fluorocompound is useful as a monomer for producing afluoropolymer excellent in physical properties such as transparency,water and oil repellency, heat resistance, mold releasability orchemical resistance. For example, a (meth)acrylate (in the presentspecification, a (meth)acrylate is a collective term of an acrylate anda methacrylate) having a polyfluoroalkyl group is useful as a monomerfor producing a fluoropolymer to be used as an antifouling agent, awater and oil repellent, a mold lubricant, etc.

In order to improve the physical properties of the above fluoropolymer,various polymerizable fluorocompounds are reported. For example, thefollowing compound wherein an acyclic perfluoroalkyl group portion and aCH₂═CClC(O)O— portion are connected via a norbornane structure, isreported (cf. Patent Document 1):

DISCLOSURE OF THE INVENTION Object to be Accomplished by the Invention

However, a polymerizable fluorocompound having a highly fluorinatednorbornane structure and its production process have been unknown.Further, a polymer obtained from such a fluorocompound and physicalproperties of such a polymer have also been unknown.

The object of the present invention is to provide a novel polymerizablepolyfluoronorbornane derivative and its production process, a novelpolymer obtained by polymerizing the polymerizable polyfluoronorbornanederivative, and an intermediate useful for the production of thefluorocompound.

Means to Accomplish the Object

The present invention has been made as a result of extensive studies toaccomplish the above object, and it provides the followings:

-   1. A compound represented by the following formula (1):

wherein the symbols in the formula have the following meanings:

Z^(A), Z^(B), Z^(C), Z^(D), and Z^(E): each of them is independently—CH(—OC(O)CT=CH₂)—, —CF(—CH₂OC(O)CT=CH₂)— or —CR^(A)R^(B)—, providedthat at least one of Z^(A) to Z^(E) is —CH(—OC(O)CT=CH₂)— or—CF(—CH₂OC(O)CT=CH₂)—, and at least one of Z^(A) to Z^(E) is—CR^(A)R^(B)— (wherein each of R^(A) and R^(B) is independently afluorine atom, a C₁₋₁₆ perfluoroalkyl group or a C₁₋₁₆ perfluoroalkylgroup containing an etheric oxygen atom, T is a hydrogen atom, afluorine atom, a C₁₋₃ alkyl group or a C₁₋₃ fluoroalkyl group);

W^(A) and W^(B): each of them is independently a fluorine atom, a C₁₋₁₆perfluoroalkyl group or a C₁₋₁₆ perfluoroalkyl group containing anetheric oxygen atom; and

n: 0, 1 or 2.

-   2. A compound represented by the following formula (1A-1):

wherein the symbols in the formula have the following meanings:

Z: —CH(—OC(O)CT¹=CH₂)— or —CF(—CH₂OC(O)CT¹=CH₂)— (wherein T¹ is ahydrogen atom, a fluorine atom, a methyl group or a trifluoromethylgroup);

W¹ and W²: each of them is independently a fluorine atom or atrifluoromethyl group; and

R¹, R², R³ and R⁴: each of them is independently a fluorine atom or aC₁₋₁₆ perfluoroalkyl group.

-   3. A compound selected from either one of compounds represented by    the following formulae:

wherein T¹ represents a hydrogen atom, a fluorine atom, a methyl groupor a trifluoromethyl group.

-   4. A process for producing a compound represented by the following    formula (1), which comprises reacting a compound represented by the    following formula (2) with a compound represented by CH₂═CTC(O)J:

wherein the symbols in the formulae have the following meanings:

Y^(A), Y^(B), Y^(C), Y^(D), and Y^(E): each of them is independently—CH(—OH)—, —CF(CH₂OH)— or —CR^(A)R^(B)—, provided that at least one ofY^(A) to Y^(E) is —CH(—OH)— or —CF(CH₂OH)—, and at least one of Y^(A) toY^(E) is —CR^(A)R^(B)—; and

Z^(A), Z^(B), Z^(C), Z^(D), and Z^(E): each of them is independently—CH(—OC(O)CT=CH₂)—, —CF(—CH₂OC(O)CT=CH₂)— or —CR^(A)R^(B)—, providedthat at least one of Z^(A) to Z^(E) is —CH(—OC(O)CT=CH₂)— or—CF(—CH₂OC(O)CT=CH₂)—, and at least one of Z^(A) to Z^(E) is—CR^(A)R^(B)—; wherein Y^(A) corresponds to Z^(A), Y^(B) to Z^(B), Y^(C)to Z^(C), Y^(D) to Z^(D) and Y^(E) to Z^(E), respectively; when each ofZ^(A) to Z^(E) is —CH(—OC(O)CT=CH₂)—, each of Y^(A) to Y^(E) is—CH(—OH)—; when each of Z^(A) to Z^(E) is —CF(—CH₂OC(O)CT=CH₂)—, each ofY^(A) to Y^(E) is —CF(CH₂OH)—; and when each of Z^(A) to Z^(E) is—CR^(A)R^(B)—, each of Y^(A) to Y^(E) is —CR^(A)R^(B)—; each of R^(A)and R^(B) is independently a fluorine atom, a C₁₋₁₆ perfluoroalkyl groupor a C₁₋₁₆ perfluoroalkyl group containing an etheric oxygen atom; and Tis a hydrogen atom, a fluorine atom, a C₁₋₃ alkyl group or a C₁₋₃fluoroalkyl group;

W^(A) and W^(B): each of them is independently a fluorine atom, a C₁₋₁₆perfluoroalkyl group or a C₁₋₁₆ perfluoroalkyl group containing anetheric oxygen atom;

J: a halogen atom; and

n: 0, 1 or 2.

-   5. A polymer which is obtained by polymerizing a compound    represented by the formula (1).-   6. The polymer according to 5, wherein its molecular weight is from    1×10³ to 1×10⁷.-   7. A compound represented by the following formula (2):

wherein the symbols in the formula have the following meanings:

Y^(A), Y^(B), Y^(C), Y^(D), and Y^(E): each of them is independently—CH(—OH)—, —CF(CH₂OH)— or —CR^(A)R^(B)—, provided that at least one ofY^(A) to Y^(E) is —CH(—OH)— or —CF(CH₂OH)—, and at least one of Y^(A) toY^(E) is —CR^(A)R^(B)— (wherein each of R^(A) and R^(B) is independentlya fluorine atom, a C₁₋₁₆ perfluoroalkyl group or a C₁₋₁₆ perfluoroalkylgroup containing an etheric oxygen atom);

W^(A) and W^(B): each of them is independently a fluorine atom, a C₁₋₁₆perfluoroalkyl group or a C₁₋₁₆ perfluoroalkyl group containing anetheric oxygen atom; and

n: 0, 1 or 2.

-   8. A compound represented by the following formula (2A-1):

wherein the symbols in the formula have the following meanings:

Y: —CH(—OH)— or —CF(—CH₂OH)—;

R¹, R², R³ and R⁴: each of them is independently a fluorine atom or aC₁₋₁₆ perfluoroalkyl group; and

W¹ and W²: each of them is independently a fluorine atom or atrifluoromethyl group.

-   9. A compound selected from compounds represented by the following    formulae:

-   10. A process for producing a compound represented by the following    formula (2), which comprises subjecting a compound represented by    the following formula (3) to a reduction reaction:

wherein the symbols in the formulae have the following meanings:

X^(A), X^(B), X^(C), X^(D) and X^(E): each of them is independently—C(O)—, —CF(C(O)G)- or —CR^(A)R^(B)—, provided that at least one ofX^(A) to X^(E) is —C(O)— or —CF(—C(O)G)-, and at least one of X^(A) toX^(E) is —CR^(A)R^(B)—;

Y^(A), Y^(B), Y^(C), Y^(D), and Y^(E): each of them is independently—CH(—OH)—, —CF(CH₂OH)— or —CR^(A)R^(B)—, provided that at least one ofY^(A) to Y^(E) is —CH(—OH)— or —CF(CH₂OH)—, and at least one of Y^(A) toY^(E) is —CR^(A)R^(B)—; wherein X^(A) corresponds to Y^(A), X^(B) toY^(B), X^(C) to Y^(C), X^(D) to Y^(D) and X^(E) to Y^(E), respectively;when each of Y^(A) to Y^(E) is —CH(—OH)—, each of X^(A) to X^(D) is—C(O)—; when each of Y^(A) to Y^(E) is —CF(—CH₂OH)—, each of X^(A) toX^(D) is —CF(—C(O)G)-; and when each of Y^(A) to Y^(E) is —CR^(A)R^(B)—each of X^(A) to X^(D) is —CR^(A)R^(B)—; each of R^(A) and R^(B) isindependently a fluorine atom, a C₁₋₁₆ perfluoroalkyl group or a C₁₋₁₆perfluoroalkyl group containing an etheric oxygen atom; G is a halogenatom or a C₁₋₁₀ alkoxy group;

W^(A) and W^(B): each of them is independently a fluorine atom, a C₁₋₁₆perfluoroalkyl group or a C₁₋₁₆ perfluoroalkyl group containing anetheric oxygen atom; and

n: 0, 1 or 2.

-   11. A compound represented by the following formula (3):

wherein the symbols in the formula have the following meanings:

X^(A), X^(B), X^(C), X^(D) and X^(E): each of them is independently—C(O)—, —CF(C(O)G)- or —CR^(A)R^(B)—, provided that at least one ofX^(A) to X^(E) is —C(O)— or —CF(—C(O)G)-, and at least one of X^(A) toX^(E) is —CR^(A)R^(B)— (wherein G is a halogen atom or a C₁₋₁₀ alkoxygroup; and each of R^(A) and R^(B) is independently a fluorine atom, aC₁₋₁₆ perfluoroalkyl group or a C₁₋₁₆ perfluoroalkyl group containing anetheric oxygen atom);

W^(A) and W^(B): each of them is independently a fluorine atom, a C₁₋₁₆perfluoroalkyl group or a C₁₋₁₆ perfluoroalkyl group containing anetheric oxygen atom; and

n: 0, 1 or 2.

-   12. A compound represented by the following formula (3A-1):

wherein the symbols in the formula have the following meanings:

X: —C(O)—, —CF(C(O)F)— or —CF(C(O)OCH₃)—;

R¹, R², R³ and R⁴: each of them is independently a fluorine atom or aC₁₋₁₆ perfluoroalkyl group; and

W¹ and W²: each of them is independently a fluorine atom or atrifluoromethyl group.

-   13. A compound selected from compounds represented by the following    formulae.

EFFECTS OF THE INVENTION

According to the present invention, a novel polymerizablepolyfluoronorbornane derivative is provided. Further, by polymerizingthe polyfluoronorbornane derivative, it is possible to obtain a polymerexcellent in heat resistance, mold releasability, chemical resistance,transparency, light resistance, water and oil repellency, low refractiveindex property, etc. Particularly, it is possible to obtain afluoropolymer excellent in dynamic water and oil repellency. Further,according to the present invention, a novel alcohol compound and a novelcarbonyl compound useful as an intermediate for production of thepolyfluoronorbornane derivative and for other applications, areprovided.

BEST MODE FOR CARRYING OUT THE INVENTION

In the present specification, a compound represented by the formula (1)is shown as a compound (1). A group represented by —CH(—OC(O)CT=CH₂)— issimply shown as —CH(—OC(O)CT=CH₂)—. Compounds and groups represented byother formulae are shown in the same manner. Further, the meanings ofthe symbols in a group are the same as the previous ones unlessotherwise specified.

Further, when a compound in the present invention has an asymmetriccarbon atom, the steric configuration of the carbon atom is notparticularly limited. With respect to a crosslinked cyclic compound inthe present invention, the steric configuration of the asymmetric centeron the main ring may be endo or exo. When a carbon atom on a main bridgeof the crosslinked cyclic compound of the present invention forms anasymmetric center, the steric configuration of the asymmetric center maybe syn or anti.

The present invention provides the following novel compound (1):

Each of Z^(A) to Z^(E) is a divalent linking group selected from—CH(—OC(O)CT=CH₂)—, —CF(—CH₂OC(O)CT=CH₂)— and —CR^(A)R^(B)—. Each of 1to 4 groups selected from Z^(A) to Z^(E) is —CH(—OC(O)CT=CH₂)— or—CF(—CH₂OC(O)CT=CH₂)—, and each of 1 to 4 groups selected from the restof Z^(A) to Z^(E) is —CR^(A)R^(B)—. Further, each of Z^(A) to Z^(E) isan independent group, and they may be the same or different. Forexample, when at least two of Z^(A) to Z^(E) are —CH(—OC(O)CT=CH₂)—, thetwo —CH(—OC(O)CT=CH₂)— may be the same groups or different groups.

Further, when at least two Z^(E)s are present in the formula (e.g. whenn is 1 or 2), Z^(E)s may be the same or different, and they arepreferably the same.

T is preferably a hydrogen atom, a fluorine atom, a methyl group or atrifluoromethyl group. T is particularly preferably a hydrogen atom or amethyl group, especially preferably a methyl group.

Each of R^(A) and R^(B) is independently preferably a fluorine atom or aC₁₋₁₆ perfluoroalkyl group. The C₁₋₁₆ perfluoroalkyl group is preferablya C₁₋₆ linear perfluoroalkyl group, particularly preferably atrifluoromethyl group. Further, it is particularly preferably a C₁₋₁₆perfluoroalkyl group wherein both of R^(A) and R^(B) are fluorine atomsor C₁₋₁₆ perfluoroalkyl groups, or one of them is a fluorine atom andthe other is a C₁₋₁₆ perfluoroalkyl group. That is, —CR^(A)R^(B)— ispreferably —CF₂—, —C(R^(F))₂— or —CFR^(F)—. R^(F) means a C₁₋₁₆perfluoroalkyl group (the same applies hereinafter).

With respect to Z^(A) to Z^(E), one or two of them are preferably groupsselected from —CH(—OC(O)CT=CH₂)— and —CF(—CH₂OC(O)CT=CH₂)—, and the restof three or four of is them are preferably —CR^(A)R^(B)—. Particularlypreferred is that one of them is —CH(—OC(O)CT=CH₂)— or—CF(—CH₂OC(O)CT=CH₂)—, and the rest of four are —CR^(A)R^(B)—.

Further, as Z^(A) to Z^(E), the following modes are preferred.

Z^(A) is —CH(—OC(O)CT=CH₂)— or —CF(—CH₂OC(O)CT=CH₂)—, and each of Z^(B)to Z^(E) is —CR^(A)R^(B)—; each of Z^(A) and Z^(B) is —CH(—OC(O)CT=CH₂)—or —CF(—CH₂OC(O)CT=CH₂)—, and each of Z^(C) to Z^(E) is —CR^(A)R^(B)—;each of Z^(A) and Z^(C) is —CH(—OC(O)CT=CH₂)— or —CF(—CH₂OC(O)CT=CH₂)—,and each of Z^(B), Z^(D) and Z^(E) is —CR^(A)R^(B)—.

With respect to Z^(A) to Z^(E), particularly preferred is that Z^(A) is—CH(—OC(O)CT=CH₂)— or —CF(—CH₂OC(O)CT=CH₂)—, and each of Z^(B) to Z^(E)is —CR^(A)R^(B)—.

Especially, when Z^(E) is —CR^(A)R^(B)—, Z^(E) is preferably —CF₂— or—C(RF)₂—, particularly preferably —CF₂— or —C(CF₃)₂—.

W^(A) and W^(B) are preferably such that each of them is a fluorineatom, or one of them is a fluorine atom and the other is atrifluoromethyl group.

n shows a repeating number of the structural unit enclosed byparenthesis [ ]. When n is 0, the compound (1) is the following compound(1A), and when n is 1, the compound (1) is the following compound (1B).When n is 2, the compound (1) is the following compound (1C).

n is preferably 0. That is, the compound (1) of the present invention ispreferably the following compound (1A).

The steric configuration of the asymmetric center on the main ring ofthe compound (1), is not particularly limited, and it may be endo orexo. When a carbon atom on the main bridge (a carbon atom in a grouprepresented by Z^(E)) of the compound (1) forms the asymmetric center,the steric configuration of the asymmetric center is not particularlylimited, and it may be syn or anti.

Further, the compound (1A) is preferably the following compound (1A-1),the following compound (1A-2) or the following compound (1A-3),particularly preferably the following compound (1A-1).

Z may be —CH(—OC(O)CT¹=CH₂)— or —CF(—CH₂OC(O)CT¹=CH₂)—. Further, two Zin the compound (1A-2) or the compound (1A-3) may be the same ordifferent.

When at least two R¹ and R² are respectively present in the formula,they may be the same or different, and they are preferably the same.Each of R¹ and R² is preferably a fluorine atom or a trifluoromethylgroup.

R³ and R⁴ are preferably such that each of them is a fluorine atom, orone of them is a fluorine atom and the other is a fluorine atom or aC₁₋₁₆ perfluoroalkyl group.

W¹ and W² are preferably such that each of them is a fluorine atom, orone of them is a fluorine atom and the other is a trifluoromethyl group.

T¹ is preferably a hydrogen atom or a methyl group.

Specific examples of the compound (1) may be the following compounds:

The compound (1) can be produced by reacting the following compound (2)with a compound represented by CH₂═CTC(O)J. The compound (2) will bedescribed later.

J is preferably a chlorine atom or a bromine atom.

Specific examples of the compound represented by CH₂═CTC(O)J may beCH₂═CHC(O)Cl, CH₂═CHC(O)Br, CH₂═C(CH₃)C(O)Cl, CH₂═C(CH₃)C(O)Br,CH₂═CFC(O)Cl, CH₂═CFC(O)Br, CH₂═C(CF₃)C(O)Cl and CH₂═C(CF₃)C(O)Br.

In the production of the compound (1), it is preferred to react from 1 kto 2 k mol of the compound represented by CH₂═CTC(O)J with 1 mol of thecompound (2) having k number in total of —CH(—OH)— and —CF(—CH₂OH)—permolecule. k is an integer of from 1 to (4+n) (the same applieshereinafter).

The reaction conditions (reaction temperature, reaction pressure,reaction time, etc.) for the above reaction are not particularlylimited, and it is preferred to follow a method and conditions known foran esterification reaction.

The compound (1) is a polymerizable compound having —CH(—OC(O)CT=CH₂)—or —CF(—CH₂OC(O)CT=CH₂)— and having a highly fluorinated norbornanestructure. Therefore, a polymer can be produced by polymerizing thecompound (1).

Further, the present invention provides a polymer obtained bypolymerizing the compound (1). The polymer of the present invention maybe a homopolymer obtained by homopolymerizing the compound (1) alone andmay be a copolymer obtained by copolymerizing the compound (1) withanother monomer (hereinafter referred to as another monomer)copolymerizable with the compound (1). In the latter case, the polymerof the present invention preferably contains from 0.1 to 99.9 mol % ofrepeating units of the compound (1) and from 0.1 to 99.9 mol % ofrepeating units of another monomer, based on the entire repeating units.Further, the copolymer preferably contains at least 50 to 99.9 mol % ofrepeating units of the compound (1) and less than 0.1 to 50 mol % ofrepeating units of another monomer.

Such another monomer is not particularly limited, and it may, forexample, be a (meth)acrylate, an unsaturated carboxylic amide, astyrene, a vinylsilane, an olefin, a fluoroolefin, a chloroolefin, avinyl ester, a vinyl ether, (meth)acrylic acid or acrylonitrile.

Specific examples of the (meth)acrylate may be an acyclic alkyl(meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate,butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl(meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, octadecyl(meth)acrylate, diethylaminoethyl (meth)acrylate, 2-hydroxyethyl(meth)acrylate or 2-hydroxypropyl (meth)acrylate; and an acyclic alkyl(meth)acrylate such as 1-adamantyl (meth)acrylate,3-hydroxyl-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl(meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 2-propyl-2-adamantyl(meth)acrylate, 2-butyl-2-adamantyl (meth)acrylate,2-oxotetrahydrofuran-3-yl (meth)acrylate, glycidyl (meth)acrylate orbenzyl (meth)acrylate.

Specific examples of the unsaturated carboxylic amide may be acrylamide,diamide itaconate, α-ethyl acrylamide, amide crotonate, diamidefumarate, diamide maleate, N-butoxymethyl acrylamide andN-methylol-acrylamide.

Specific examples of the styrene may be styrene, α-methylstyrene,chlorostyrene and hydroxystyrene.

Specific examples of the vinylsilane may be vinyl methyldimethoxysilane, vinyl methyl diethoxysilane, vinyl methyldichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane and vinyltrichlorosilane.

Specific examples of the olefin may be ethylene, propylene andisobutylene.

Specific examples of the fluoroolefin may be an acyclic fluoromonoenesuch as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene orhexafluoropropylene; a cyclic fluoromonoene such asperfluoro(2,2-dimethyl-1,3-dioxole) orperfluoro(2-methylene-1,3-dioxolane); and a fluorodiene such asCF₂═CFOCF₂CF₂CF═CF₂, CF₂═CFOCF₂CF(CF₃)CF═CF₂, CF₂═CFOCF(CF₃)CF₂CF═CF₂,CF₂═CFCF₂C(CF₃)(OH)CH₂CH═CH₂ or CF₂═CFCH₂CH(C(CF₃)₂OH)CH₂CH═CH₂.

Specific examples of the chloroolefin may be vinyl chloride, vinylidenechloride and chloroprene.

Specific examples of the vinyl ester may be vinyl acetate and vinylpropionate.

Specific examples of the vinyl ether may be 2-hydroxyvinyl ether andaminoethyl vinyl ether.

The polymerization of the compound (1) is preferably carried out in thepresence of a polymerization initiator. Specific examples of thepolymerization initiator may be an organic peroxide such as(C₆H₅C(O)O—)₂, (C₆F₅C(O)O—)₂, (C₃F₇C(O)O—)₂, ((CH₃)₃CC(O)—)₂,((CH₃)₂CHC(O)O—)₂, ((CH₃)₃C(O)C(O)O—)₂, ((CH₃)₃C(O)O—)₂,((CH₃)₂CHOC(O)O—)₂ or ((CH₃)₃CC₆H₁₀OC(O)O—)₂, an azo compound such asazobisisobutyronitrile, and an inorganic peroxide.

The polymerization conditions (polymerization temperature,polymerization pressure, etc.) in the polymerization of the compound (1)are not particularly limited. The polymerization temperature ispreferably from 0 to 200° C. The polymerization pressure is preferablyfrom atmospheric pressure to 10 MPa (gauge pressure).

The weight average molecular weight of the polymer of the presentinvention is preferably from 1×10³ to 1×10⁷, more preferably from 1×10³to 1×10⁵.

The polymer of the present invention is a polymer excellent intransparency, water and oil repellency, heat resistance, moldreleasability, chemical resistance and particularly dynamic waterrepellency. The polymer of the present invention is useful as anantifouling agent, a water and oil repellent, a mold lubricant, anoptical fiber material, a pellicle material, a lens material, a surfaceprotecting material for a display.

Further, the preferred mode of the polymer of the present invention maybe a polymer which is obtained by homopolymerizing the compound (1)alone, and which is made of only repeating units of the compound (1) andhas a weight average molecular weight of from 1,000 to 50,000. Therepeating units in the present specification mean units formed bypolymerization of a polymerizable compound such as the compound (1).

The following compound (2) as an intermediate for production of thecompound (1) is a novel compound having a hydroxyl group or ahydroxymethyl group and having a highly fluorinated norbornanestructure. In addition to being useful as an intermediate for productionof the compound (1), the compound (2) can be converted to variousderivatives by utilizing the reactivity of hydroxyl groups in Y^(A) toY^(E). Since every converted compound has a highly fluorinatednorbornane structure, the compound exhibits performance such as waterand oil repellency, which is derived from the structure. That is, thepresent invention provides the following novel compound (2).

Y^(A), Y^(B), Y^(C), Y^(D), and Y^(E) are as defined above, and theirpreferred modes are as follows.

Y^(A) is —CH(—OH)— or —CF(—CH₂OH)—, and each of Y^(B), Y^(C), Y^(D) andY^(E) is —CR^(A)R^(B)—; each of Y^(A) and Y^(B) is —CH(—OH)— or—CF(—CH₂OH)—, and each of Y^(C), Y^(D) and Y^(E) is —CR^(A)R^(B)—; andeach of Y^(A) and Y^(C) is —CH(—OH)— or —CF(—CH₂OH)—, and each of Y^(B),Y^(D) and Y^(E) is —CR^(A)R^(B)—.

Further, it is particularly preferred that Y^(A) is —CH(—OH)— or—CF(—CH₂OH)—, and each of Y^(B), Y^(C), Y^(D) and Y^(E) is—CR^(A)R^(B)—.

Here, R^(A) and R^(B) are as defined above, and they may be the same ordifferent. Each of R^(A) and R^(B) is independently preferably afluorine atom or a C₁₋₁₆ perfluoroalkyl group. Particularly preferred isthat both of them are fluorine atoms or C₁₋₁₆ perfluoroalkyl groups, orthat one of them is a fluorine atom, and the other is a C₁₋₁₆perfluoroalkyl group. That is, —CR^(A)R^(B)— is preferably —CF₂—,—C(R^(F))₂— or —CFR^(F)—.

When Z^(E) is —CR^(A)R^(B)—, Z^(E) is preferably —CF₂— or —C(RF)₂—,particularly preferably —CF₂— or —C(CF₃)₂—.

W^(A) and W^(B) are independent of each other, and they may be the sameor different. When at least two W^(A)s are present in a molecule, theymay be the same or different. The same applies to W^(B). W^(A) and W^(B)are preferably such that each of them is a fluorine atom, or one of themis a fluorine atom and the other is a trifluoromethyl group.

n has the same meaning as above, and n is preferably 0. When n is 0, thecompound (2) is the following compound (2A), and when n is 1, thecompound (2) is the following compound (2B). When n is 2, the compound(2) is the following compound (2C).

The steric configuration of the asymmetric center on the main ring ofthe compound (2) is not particularly limited, and it may be endo or exo.When a carbon atom on the main bridge (a carbon atom in a grouprepresented by Y^(E)) of the compound (2) forms the asymmetric center,the steric configuration of the symmetric center is not particularlylimited, and it may be syn or anti.

The compound (2) is preferably the following compound (2A-1), thefollowing compound (2A-2) or the following compound (2A-3), particularlypreferably the following compound (2A-1).

Y is —CH(—OH)— or —CF(—CH₂OH)—. Two Ys in the compound (2A-2) or thecompound (2A-2) may be the same or different.

Each of R¹ and R² is preferably a fluorine atom or a trifluoromethylgroup.

R³ and R⁴ are preferably such that each of them is a fluorine atom, orone of them is a fluorine atom and the other is a fluorine atom or aC₁₋₁₆ perfluoroalkyl group.

W¹ and W² are preferably such that each of them is a fluorine atom, orone of them is a fluorine atom and the other is a trifluoromethyl group.

Specific examples of the compound (2) may be the following compounds.

The compound (2) can be produced by subjecting the following compound(3) to a reduction reaction. The detail of the compound (3) will bedescribed later.

The reduction reaction of the compound (3) is preferably carried out bya reaction between the compound (3) with a reducing agent. The reducingagent is not particularly limited, and it is preferably NaBH₄, atetrahydrofuran solution of B₂H₆, a hexane solution of((CH₃)₂CHCH₂)₂AlH, or LiAlH₄.

The reduction reaction is preferably carried out by reacting from 1 k to2 k mol of the reducing agent with 1 mol of the compound (3) having knumber in total of —C(O)— and —CF(—C(O)G)- in one molecule.

The reaction conditions (reaction temperature, reaction pressure,reaction time, etc.) for the reduction reaction are not particularlylimited. For example, it is preferably carried out in accordance with amethod described in a paragraph 0021 of JP-A-10-72568, wherein acylfluoride (—COF) is esterified to methyl ester (—COOCH₃) or the like,followed by reduction with NaBH₄, to obtain an alcohol (—CH₂OH).

The compound (3) is a novel compound having —C(O)— or —CF(—C(O)G)- and ahighly fluorinated norbornane structure. The compound (3) is useful e.g.as an intermediate for production of the compound (2). That is, thepresent invention provides the following novel compound (3).

X^(A), X^(B), X^(C), X^(D) and X^(E) are as defined above, and thefollowing modes are preferred. That is, X^(A) is —C(O)— or —CF(—C(O)G)-,and each of X^(B), X^(C), X^(D) and X^(E) is —CR^(A)R^(B)—; each ofX^(A) and X^(B) is —C(O)— or —CF(—C(O)G)-, and each of X^(C), X^(D) andX^(E) is —CR^(A)R^(B)—; each of X^(A) and X^(C) is —C(O)— or—CF(—C(O)G)-, and each of X^(B), X^(D) and X^(E) is —CR^(A)R^(B)—.Further, particularly preferred is that X^(A) is —C(O)— or —CF(—C(O)G)-,and that each of X^(B), X^(C), X^(D) and X^(E) is —CR^(A)R^(B)—.

G is preferably a fluorine atom or a C₁₋₁₀ alkoxy group, particularlypreferably a fluorine atom or a methoxy group.

Each of R^(A) and R^(B) is independently preferably a fluorine atom or aC₁₋₁₆ perfluoroalkyl group. Particularly preferred is that both of themare fluorine atoms or C₁₋₁₆ perfluoroalkyl groups, or that one of themis a fluorine atom, and the other is a C₁₋₁₆ perfluoroalkyl group. Thatis, —CR^(A)R^(B)— is preferably —CF₂—, —C(R^(F))₂— or —CFR^(F)—. Here,R^(F) means a C₁₋₁₆ perfluoroalkyl group.

When Z^(E) is —CR^(A)R^(B)—, Z^(E) is preferably —CF₂— or —C(R^(F))₂,particularly preferably —CF₂— or —C(CF₃)₂—.

W^(A) and W^(B) are preferably such that each of them is a fluorineatom, or one of them is a fluorine atom and the other is atrifluoromethyl group.

n has the same meaning as above. n is preferably 0. When n is 0, thecompound (3) is the following compound (3A), and when n is 1, thecompound (3) is the following compound (3B). When n is 2, the compound(3) is the following compound (3C).

The steric configuration of the asymmetric center on the main ring ofthe compound (3) is not particularly limited, and it may be endo or exo.When a carbon atom on the main bridge (a carbon atom in a grouprepresented by X^(E)) of the compound (3) forms the asymmetric center,the steric configuration of the symmetric center is not particularlylimited, and it may be syn or anti.

The compound (3) is preferably the following compound (3A-1), thefollowing compound (3A-2) or the following compound (3A-3), particularlypreferably the following compound (3A-1).

X is —C(O)—, —CF(—C(O)F)— or —CF(—C(O)OCH₃)—. Two Xs in the compound(3A-2) or in the compound (3A-3) may be the same or different.

Each of R¹ and R² is preferably a fluorine atom or a trifluoromethylgroup.

R³ and R⁴ are preferably such that each of them is a fluorine atom, orone of them is a fluorine atom and the other is a fluorine atom or aC₁₋₁₆ perfluoroalkyl group.

W¹ and W² are preferably such that each of them is a fluorine atom, orone of them is a fluorine atom and the other is a trifluoromethyl group.

Specific examples of the compound (3) may be the following compounds.

The compound (3) can be produced in such a manner that the followingcompound (6) and a compound represented by R^(f)—C(O)F are subjected toan esterification reaction to obtain the following compound (5), andthen, the compound (5) is subjected to a fluorination reaction to obtainthe following compound (4), followed by a thermal decomposition reactionof the compound (4), in the presence of an alkali metal fluoride.Further, it can also be produced by reacting the compound (4) with aC₁₋₁₀ alkanol.

wherein the symbols in the formulae have the following meanings:

Each of X^(FA), X^(FB), X^(FC), X^(FD) and X^(FE): —CF(—OC(O)R^(f))—,—CF(—CF₂OC(O)R^(f))— or —CR^(A)R^(B)—. However, X^(FA) is a groupcorresponding to X^(A), X^(FB) to X^(B), X^(FC) to X^(C), X^(FD) toX^(D) and X^(FE) to X^(E), respectively; a group corresponding to —C(O)—is —CF(—OC(O)R^(f))—, a group corresponding to —C(—C(O)G)- is—CF(—CF₂OC(O)R^(f))—, and a group corresponding to —CR^(A)R^(B)— is—CR^(A)R^(B)—.

Each of X^(HA), X^(HB), X^(HC), X^(HD) and X^(HE): —CH(O)R^(f))—,—CH(—CH₂OC(O)R^(f)— or —CR^(HA)R^(HB)—. However, X^(HA) is a groupcorresponding to X^(FA), X^(HB) to X^(FB). X^(HC) to X^(FC), X^(HD) toX^(FD) and X^(HE) to X^(FE), respectively; a group corresponding to—CF(—OC(O)R^(f))— is —CH(—OC(O)R^(f))—, a group corresponding to—CF(CF₂OC(O)R^(f))— is —CH(—CH₂OC(O)R^(f))—, and a group correspondingto —CR^(HA)R^(HB)— is —CR^(HA)R^(HB)—. Further, between X^(HC) andX^(HD), a carbon atom-carbon atom double bond may be formed.

Each of X^(LA), X^(LB), X^(LC), X^(LD) and X^(LE): —CH(—OH)—,—CH(—CH₂OH)— or —CR^(HA)R^(HB)—. However, X^(LA) is a groupcorresponding to X^(HA), X^(LB) to X^(HB), X^(LC) to X^(HC), X^(LD) toX^(HD) and X^(LE) to X^(HE), respectively; a group corresponding to—CH(—OC(O)R^(f))— is —CH(OH)—, a group corresponding to—CH(—CH₂OC(O)R^(f))— is —CH(—CH₂OH)— and a group corresponding to—CR^(HA)R^(HB)— is —CR^(HA)R^(HB)—. Further, a carbon-carbon bondbetween X^(LC) and X^(LD) may be a double bond.

Each of W^(HA) and W^(HB): a hydrogen atom, a C₁₋₁₆ alkyl group or aC₁₋₁₆ alkyl group containing an etheric oxygen atom. However, W^(HA) isa group corresponding to W^(A), W^(HB) to W^(B); a group correspondingto a fluorine atom is a hydrogen atom; a group corresponding to a C₁₋₁₆perfluoroalkyl group is a C₁₋₁₆ alkyl group; a group corresponding to aC₁₋₁₆ perfluoroalkyl group containing an etheric oxygen atom is a C₁₋₁₆alkyl group containing an etheric oxygen atom.

Each of R^(HA) and R^(HB): a hydrogen atom, a C₁₋₁₆ alkyl group or aC₁₋₁₆ alkyl group containing an etheric oxygen atom. However, R^(HA) isa group corresponding to R^(A), R^(HB) to R^(B), R^(HC) to R^(C), R^(HD)to R^(D) and R^(ED) to R^(E), respectively; a group corresponding to afluorine atom is a hydrogen atom; a group corresponding to a C₁₋₁₆perfluoroalkyl group is a C₁₋₁₆ alkyl group; and a group correspondingto a C₁₋₁₆ perfluoroalkyl group containing an etheric oxygen atom is aC₁₋₁₆ alkyl group containing an etheric oxygen atom.

R^(f): a C₁₋₂₀ perfluoroalkyl group or a C₁₋₂₀ perfluoroalkyl groupcontaining an etheric oxygen atom.

Specific examples of the compound (6) may be the following compounds.The compound (6) is a known compound or a compound obtainable by a knownmethod.

Specific examples of the compound represented by R^(f)—C(O)F may beCF₃C(O)F, (CF₃)₂CFC(O)F, F(CF₂)₃OCF(CF₃)C(O)F andF(CF₂)₃OCF(CF₃)CF₂OCF(CF₃)C(O)F.

Specific examples of the compound (5) may be the following compounds.

Specific examples of the compound (4) may be the following compounds.

The respective reaction conditions for an esterification reaction of thecompound (6) with the compound represented by R^(f)—C(O)F, afluorination reaction of the compound (5) and a thermal decompositionreaction of the compound (4), are preferably the reaction conditionsdescribed in WO00/56694, WO02/18314, etc.

According to the present invention, a novel polymerizable compound andpolymer can be provided. The polymer of the present invention has astructure wherein a highly fluorinated norbornane structure is hanged ona side chain, whereby the polymer exhibits excellent water and oilrepellency, heat resistance, mold releasability, chemical resistance,transparency, durability, light resistance and low refractive indexproperty. The polymer provided by the present invention is particularlyexcellent in dynamic water and oil repellency, especially excellent indynamic water repellency, and that is, it is a polymer having anexcellent property such that the contact angle with water is at least80°, and the sliding angle is at most 20°. The polymer of the presentinvention is useful for various applications, in which such propertiesare required.

EXAMPLES

In Examples, 1,1,2-trichloro-1,2,2-trifluoroethane is shown as R113,dichloropentafluoropropane as R225, tetrahydrofuran as THF, andtetramethylsilane as TMS. As R225, a mixture of CF₃CF₂CHCl₂ andCF₂ClCF₂CHFCl, was used.

Example 1 Production Example of Compound (31)

By following a production route represented by the following formula, acompound (31) was produced from the following compound (61). Here, acompound represented by R^(f1)—COF is F(CF₂)₃OCF(CF₃)CF₂OCF(CF₃)C(O)F.

Into a flask under a nitrogen gas atmosphere, 15 g of the compound (61),100 g of chloroform and 7.02 g of NaF were introduced, and while insideof the flask was cooled with ice and was stirred, 79 g of the compoundrepresented by R^(f1)—COF was dropwise added thereto. After inside ofthe flask was further stirred, an insoluble solid in the content of theflask was removed by pressure filtration. Into the content of the flask,103 g of saturated sodium hydrogen carbonate aqueous solution was added.An organic layer of the formed two-layer separated liquid was recovered.The recovered organic layer was concentrated to obtain 74 g of acompound (51).

Then, into an autoclave (made of nickel, inner volume: 500 mL) having aNaF pellet packed bed set at a gas outlet, 313 g of R113 was added, andwhile stirring inside of the autoclave at 25° C., nitrogen gas was blowninto the autoclave for 1 hour. Further, fluorine gas diluted to 20%volume with nitrogen gas (hereinafter referred to as 20% fluorine gas)was blown therein.

While the 20% fluorine gas was continuously blown therein, under apressure of 0.1 MPa (gauge pressure), a solution having 67 g of thecompound (51) dissolved in 299 g of R113, was introduced in theautoclave. After completion of the introduction, nitrogen gas was blowninto the autoclave. Then, the content in the autoclave was recovered andconcentrated to obtain a compound (41).

Then, into a flask under a nitrogen gas atmosphere, 80 g of the compound(41) and 0.7 g of a KF powder were introduced, and while the innertemperature of the flask was raised to from 80 to 120° C., the flask washeated for 6 hours. The content of the flask was purified by using adistillation method using a cold trap and a recrystallization method, toobtain 38 g of white solid compound (31).

The NMR data of the compound (31) are shown as follows.

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −116.8(1F), −118.2 (1F), −122.9 (1F), −123.3 (1F), −125.4 (1F), −127.3 (1F),−130.6 (1F), −134.6 (1F), −219.4 (1F), −227.5 (1F).

Example 2 Production Example of Compound (21)

Into a round-bottom flask (inner volume: 100 mL) under a nitrogen gasatmosphere, 1.1 g of NaBH₄ and 30 g of THF were introduced. While theflask was cooled with ice and was stirred, 48 g of an R225 solutioncontaining 22 mass % of the compound (31) was dropwise added into theflask, over 1.5 hours. After completion of the dropwise addition, insideof the flask was stirred for further 30 minutes. Further, while keepingthe inner temperature of the flask at 25° C., inside of the flask wasstirred for 12 hours. Then, the liquid content of the flask wasneutralized with 0.1 mol/L of a hydrochloric acid aqueous solution (150mL), followed by washing with water. The resultant was distilled andpurified to obtain the following compound (21).

The NMR data of the compound (21) are shown as follows.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 4.89 to 4.57(2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −105.0(1F), −119.7 (1F), −124.0 (1F), −124.3 (1F), −125.7 (1F), −126.8 (1F),−133.2 (2F), −216.6 (1F), −223.5 (1F).

Example 3 Production Example of Compound (11)

Into a flask, 2.2 g of the compound (21), 10 g of THF, 2 mg of analuminum salt of N-nitrosophenyl hydroxyamine and 1.2 g of triethylaminewere introduced. The flask was cooled with ice, and with stirring, 7.3 gof a THF solution of a compound represented by CH₂═C(CH₃)C(O)Cl (1.2 g)was slowly dropwise added into the flask. After completion of thedropwise addition, inside of the flask was stirred for 2 hours, andthen, 30 mL of a sodium hydrogencarbonate aqueous solution was addedthereto.

The extraction liquid obtained by extracting the liquid content of theflask with R225, was dried over anhydrous sodium sulfate, and then,concentrated to obtain a concentrated liquid. The concentrated liquidwas purified by a silica gel column chromatography to obtain 2.7 g ofthe following compound (11).

The NMR data of the compound (11) are shown as follows.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 6.31 (1H),5.88 (1H), 5.84 (1H), 2.01 (3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −104.6(1F), −120.5 (1F), −122.4 (1F), −124.2 (1F), −124.6 (1F), −126.5 (1F),−132.7 to −132.8 (2F), −214.8 (1F), −223.2 (1F).

Example 4 Production Example of Compound (32^(M))

By following the production route represented by the following formula,a compound (32^(M)) was produced from the following compound (62). Here,a compound represented by R^(f2)—C(O)F is a compound represented byF(CF₂)₃OCF(CF₃)C(O)F.

Into a flask under a nitrogen gas atmosphere, 26 g of the compound (62)and 100 g of R225 were introduced. With cooling with ice, 91 g of thecompound represented by R^(f2)—C(O)F was dropwise added thereto whilestirring inside of the flask. Inside of the flask was further stirred,and then, the content was concentrated and filtrated to obtain 88 g ofcompound (52).

Then, into an autoclave (made of nickel, inner volume: 500 mL) having aNaF pellet packed bed set at a gas outlet, 326 g of R113 was added, andwhile stirring inside of the autoclave at 25° C., a nitrogen gas wasblown into the autoclave for 1 hour. Further, 20% fluorine gas was blowntherein.

While the 20% fluorine gas was continuously blown therein, under apressure of 0.1 MPa (gauge pressure), a solution having 75 g of thecompound (52) dissolved in 346 g of R113, was introduced in theautoclave. After completion of the introduction, a nitrogen gas wasblown into the autoclave. Then, the autoclave content was recovered andconcentrated to obtain a compound (42).

Under cooling with ice, 20 g of methanol was dropwise added to asolution obtained by dissolving 106 g of the compound (42) into 100 mLof R225. After completion of the dropwise addition, at a solutiontemperature of 25° C., the solution was stirred for 12 hours. R225 andF(CF₂)₃OCF(CF₃)COOCH₃ were distilled from the solution to obtain 42 g ofa compound (32^(M)).

The NMR data of the compound (32^(M)) are shown as follows.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 3.97 (3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −116.4 to−132.2 (8F), −174.3 (1F), −219.1 (1F), −227.0 (1F).

Example 5 Production Example of Compound (32^(F))

Into a flask having a simple distillation apparatus set on its upperpart, 100 g of the compound (42) obtained in the same manner as inExample 4 and 1.7 g of a KF powder were introduced. When the innertemperature of the flask was adjusted to be at 80° C. and inside of theflask was stirred, reflux of the liquid content of the flask wasobserved. While having F(CF₂)₃OCF(CF₃)COF distilled by the simpledistillation apparatus, inside of the flask was stirred for 5 hours.After completion of the distillation to the simple distillationapparatus, the flask was gradually cooled, and R225 and R113 wereintroduced in the flask. Then, as a result of analyzing the reactionproduct obtained by removing KF in the liquid content of the flask bypressure filtration, the formation of the following compound (32^(F))was confirmed. The yield calculated from ¹⁹F-NMR was 96%.

The NMR data of the compound (32^(F)) are as follows.

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): +39.3 to+35.6 (1F), −117.5 to −132.0 (8F), −178.8 (1F), −218.0 to −226.2 (2F).

Example 6 Production Example of Compound (22)

Into an ice-cooled solution obtained by dissolving 42 g of the compound(32^(M)) into 100 mL of THF, 20 g of a hexane solution containing 79mass % of ((CH₃)₂CHCH₂)₂AlH was dropwise added. After completion of thedropwise addition, the solution was stirred at 25° C. for 12 hours, andthen, the solution was neutralized with 0.2 mol/L hydrochloric aqueoussolution (150 mL) to obtain a reaction crude liquid.

The reaction crude liquid was extracted with R225 to obtain anextraction liquid, and a low-boiling component of the extraction liquidwas distilled to obtain 31 g of a white solid reaction product. Thereaction product was recrystallized in hexane to obtain the followingcompound (22) of a capillary crystal (colorless).

The NMR data of the compound (22) are as follows.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 4.20 (2H, dd,j=24.9 and 6.6 Hz), 2.15 (1H, m).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −119.3(1F), −121.3 (1F), −123.5 (1F), −123.6 (1F), −124.6 (1F), −125.0 (1F),−128.7 (1F), −131.6 (1F), −183.2 (1F), −220.2 (1F), −227.1 (1F).

Example 7 Production Example of Compound (12)

Into a flask, 16.3 g of the compound (22), 82 mL of tert-butyl methylether, 5 mg of hydroquinone and 8.1 g of triethylamine were introduced.While cooling inside of the flask with ice and stirring, 8.4 g ofCH₂═C(CH₃)C(O)Cl was dropwise added into the flask. After completion ofthe dropwise addition, inside of the flask was further stirred for 17hours, and then, 50 mL of pure water was introduced in the flask. Thesalt precipitated in the flask was dissolved to obtain a two-layerseparated liquid.

The upper layer (a tert-butyl methyl ether layer) of the content of theflask was recovered, and the recovered liquid was dried over anhydroussodium sulfate and was concentrated to obtain a concentrated liquid. Theconcentrated liquid was purified by a silica gel column chromatographyto obtain 14 g of the following compound (12).

The NMR data of the compound (12) are as follows.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 6.20 (1H),5.70 (1H), 4.75 (2H), 1.98 (3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −118.6(1F), −120.6 (1F), −123.8 (2F), −124.5 (1F), −124.9 (1F), −128.6 (1F),−131.4 (1F), −179.1 (1F), −219.8 (1F), −227.0 (1F).

Example 8 Polymerization Example of Compound (11)

Into a pressure-proof reactor (inner volume: 30 mL), 3.0 g of thecompound (11), 11.3 g of R225 and 1.5 g of diisopropylperoxycarbonatewhich was diluted to 50 mass % by R225, were introduced. Inside of thereactor was frozen and degassed, and then, the inner temperature of thereactor was adjusted to 40° C., and a polymerization reaction wascarried out for 18 hours. After the polymerization reaction, the contentliquid of the reactor was dropwise added to methanol, the formed solidproduct was recovered, and the solid product was vacuum dried at 90° C.for 15 hours. As a result, 2.2 g of a polymer formed by polymerizationof the compound (11) (hereinafter referred to as a polymer (11)) wasobtained. The formation of the polymer can be confirmed according to thefact that the compound (11) could hardly be detected by an NMRmeasurement of the liquid content, and there was no absorption based ona methacryloyl group in IR of the product. The polymer (11) was a whitesolid polymer at 25° C.

The molecular weight of the polymer (11) was measured by a gelpermeation chromatography method wherein a solvent mixture made of 99vol % of R225 and 1 vol % of hexafluoropropanol, was referred to as amobile phase, and polymethyl methacrylate was referred to as an innerstandard. The number average molecular weight of the polymer (11) was4,600, and the weight average molecular weight was 8,800. Further, thecontact angle of the polymer (11) to water was 107°, and its slidingangle was 9°.

The measurements of the contact angle and the sliding angle were carriedout by the following process. That is, a solution having the polymer(11) dissolved in 1,3-bis(trifluoromethyl)benzene, was prepared. Thesolution was filtrated to obtain a solution containing 4 mass % of thepolymer (11) based on the total mass of 1,3(trifluoromethyl)benzene.Then, the solution was applied on a surface of a silicon substrate bycarrying out a spin coating method (rotation condition: 2,000 rpm for 30seconds). Further, by heating the substrate at least to the boilingpoint of the solvent, the solvent was removed, and a film of the polymer(11) was formed on the surface of the silicon substrate. Then, a dropletof water (2 μL) was placed on the film, and in a state of keeping thesubstrate in horizontal, the contact angle of the droplet of water tothe film, was measured. Further, a droplet of water (50 μL) at 25° C.was placed on the film, and by declining the substrate, the inclinationangle of the substrate immediately before the droplet of water fell, wasmeasured. Such value was referred to as a sliding angle. Suchmeasurements were carried out by using a contact angle meter (tradename:DropMaster700, manufactured by Kyowa Interface Science Co., Ltd.).

Example 9 Polymerization Example of Compound (12)

Into a pressure-proof reactor (inner volume: 30 mL), 2.0 g of thecompound (12), 10.7 g of R225 and 1.3 g of diisopropylperoxycarbonatewhich was diluted to 50 mass % by R225, and 0.35 g of isopropyl alcohol,were introduced. Inside of the reactor was frozen and degassed, andthen, the inner temperature of the reactor was adjusted to 40° C., and apolymerization reaction was carried out for 18 hours. After thepolymerization reaction, the liquid content of the reactor was dropwiseadded to methanol to recover the formed solid product, and the solidproduct was vacuum dried at 90° C. for 15 hours. As a result, 1.2 g of apolymer formed by polymerization of the compound (12) (hereinafterreferred to as a polymer (12)), was obtained. The polymer (12) was awhite solid polymer at 25° C.

As a result of measuring the molecular weight of the polymer (12) in thesame manner as in Example 8, the number average molecular weight of thepolymer (12) was 4,300, and the weight average molecular weight was8,800. Further, the contact angle of the polymer (12) to water was 106°,and the sliding angle was 11°.

INDUSTRIAL APPLICABILITY

According to the present invention, a novel fluorocompound having ahighly fluorinated norbornane structure, is provided. A polymer obtainedby polymerizing the polymerizable compound having the fluorinatednorbornane structure, of the present invention, is excellent in waterand oil repellency, heat resistance, mold releasability, chemicalresistance, transparency, durability and light resistance and lowrefractive index property, and it is a polymer particularly excellent indynamic water and oil repellency. The polymer of the present inventionis useful as an antifouling agent, a water and oil repellent, a moldlubricant, an optical fiber material, a pellicle material, a lensmaterial, a display surface protection film, etc.

The entire disclosure of Japanese Patent Application No. 2006-190484filed on Jul. 11, 2006 including specification, claims and summary isincorporated herein by reference in its entirety.

What is claimed is:
 1. A compound represented by the following formula(1):

wherein the symbols in the formula have the following meanings: Z^(A),Z^(B), Z^(C), Z^(D), and Z^(E): each of them is independently—CH(—OC(O)CT═CH₂)—, —CF(—CH₂OC(O)CT═CH₂)— or —CR^(A)R^(B)—, providedthat at least one of Z^(A) to Z^(E) is —CH(—OC(O)CT═CH₂)— or—CF(—CH₂OC(O)CT═CH₂)—, and at least one of Z^(A) to Z^(E) is—CR^(A)R^(B)— (wherein each of R^(A) and R^(B) is independently afluorine atom, a C₁₋₁₆ perfluoroalkyl group or a C₁₋₁₆ perfluoroalkylgroup containing an etheric oxygen atom, T is a hydrogen atom, afluorine atom, a C₁₋₃ alkyl group or a C₁₋₃ fluoroalkyl group); W^(A)and W^(B): each of them is independently a fluorine atom, a C₁₋₁₆perfluoroalkyl group or a C₁₋₁₆ perfluoroalkyl group containing anetheric oxygen atom; and n: 0, 1 or
 2. 2. A compound represented by thefollowing formula (1A-1):

wherein the symbols in the formula have the following meanings: Z:—CH(—OC(O)CT¹═CH₂)— or —CF(—CH₂OC(O)CT¹═CH₂)— (wherein T¹ is a hydrogenatom, a fluorine atom, a methyl group or a trifluoromethyl group); W¹and W²: each of them is independently a fluorine atom or atrifluoromethyl group; and R¹, R², R³ and R⁴: each of them isindependently a fluorine atom or a C₁₋₁₆ perfluoroalkyl group.
 3. Acompound selected from either one of compounds represented by thefollowing formulae:

wherein T¹ represents a hydrogen atom, a fluorine atom, a methyl groupor a trifluoromethyl group.
 4. A process for producing a compoundrepresented by the following formula (1), which comprises reacting acompound represented by the following formula (2) with a compoundrepresented by CH₂═CTC(O)J:

wherein the symbols in the formulae have the following meanings: Y^(A),Y^(B), Y^(C), Y^(D), and Y^(E): each of them is independently —CH(—OH)—,—CF(CH₂OH)— or —CR^(A)R^(B)—, provided that at least one of Y^(A) toY^(E) is —CH(—OH)— or —CF(CH₂OH)—, and at least one of Y^(A) to Y^(E) is—CR^(A)R^(B)—; and Z^(A), Z^(B), Z^(C), Z^(D), and Z^(E): each of themis independently —CH(—OC(O)CT═CH₂)—, —CF(—CH₂OC(O)CT═CH₂)— or—CR^(A)R^(B)—, provided that at least one of Z^(A) to Z^(E) is—CH(—OC(O)CT═CH₂)— or —CF(—CH₂OC(O)CT═CH₂)—, and at least one of Z^(A)to Z^(E) is —CR^(A)R^(B)—; wherein Y^(A) corresponds to Z^(A), Y^(B) toZ^(B), Y^(C) to Z^(C), Y^(D) to Z^(D) and Y^(E) to Z^(E), respectively;when each of Z^(A) to Z^(E) is —CH(—OC(O)CT═CH₂)—, each of Y^(A) toY^(E) is —CH(—OH)—; when each of Z^(A) to Z^(E) is—CF(—CH₂OC(O)CT═CH₂)—, each of Y^(A) to Y^(E) is —CF(CH₂OH)—; and wheneach of Z^(A) to Z^(E) is —CR^(A)R^(B)—, each of Y^(A) to Y^(E) is—CR^(A)R^(B)—; each of R^(A) and R^(B) is independently a fluorine atom,a C₁₋₁₆ perfluoroalkyl group or a C₁₋₁₆ perfluoroalkyl group containingan etheric oxygen atom; and T is a hydrogen atom, a fluorine atom, aC₁₋₃ alkyl group or a C₁₋₃ fluoroalkyl group; W^(A) and W^(B): each ofthem is independently a fluorine atom, a C₁₋₁₆ perfluoroalkyl group or aC₁₋₁₆ perfluoroalkyl group containing an etheric oxygen atom; J: ahalogen atom; and n: 0, 1 or
 2. 5. A compound represented by thefollowing formula (2):

wherein the symbols in the formula have the following meanings: Y^(A),Y^(B), Y^(C), Y^(D), and Y^(E): each of them is independently —CH(—OH)—,—CF(CH₂OH)— or —CR^(A)R^(B)—, provided that at least one of Y^(A) toY^(E) is —CH(—OH)— or —CF(CH₂OH)—, and at least one of Y^(A) to Y^(E) is—CR^(A)R^(B)— (wherein each of R^(A) and R^(B) is independently afluorine atom, a C₁₋₁₆ perfluoroalkyl group or a C₁₋₁₆ perfluoroalkylgroup containing an etheric oxygen atom); W^(A) and W^(B): each of themis independently a fluorine atom, a C₁₋₁₆ perfluoroalkyl group or aC₁₋₁₆ perfluoroalkyl group containing an etheric oxygen atom; and n: 0,1 or
 2. 6. A compound represented by the following formula (2A-1):

wherein the symbols in the formula have the following meanings: Y:—CH(—OH)— or —CF(—CH₂OH)—; R¹, R², R³ and R⁴: each of them isindependently a fluorine atom or a C₁₋₁₆ perfluoroalkyl group; and W¹and W²: each of them is independently a fluorine atom or atrifluoromethyl group.
 7. A compound selected from compounds representedby the following formulae:


8. A process for producing a compound represented by the followingformula (2), which comprises subjecting a compound represented by thefollowing formula (3) to a reduction reaction:

wherein the symbols in the formulae have the following meanings: X^(A),X^(B), X^(C), X^(D) and X^(E): each of them is independently —C(O)—,—CF(C(O)G)- or —CR^(A)R^(B)—, provided that at least one of X^(A) toX^(E) is —C(O)— or —CF(—C(O)G)- , and at least one of X^(A) to X^(E) is—CR^(A)R^(B)—; Y^(A), Y^(B), Y^(C), Y^(D), and Y^(E): each of them isindependently —CH(—OH)—, —CF(CH₂OH)— or —CR^(A)R^(B)—, provided that atleast one of Y^(A) to Y^(E) is —CH(—OH)— or —CF(CH₂OH)—, and at leastone of Y^(A) to Y^(E) is —CR^(A)R^(B)—; wherein X^(A) corresponds toY^(A), X^(B) to Y^(B), X^(C) to Y^(C), X^(D) to Y^(D) and X^(E) toY^(E), respectively; when each of Y^(A) to Y^(E) is —CH(—OH)—, each ofX^(A) to X^(D) is —C(O)—; when each of Y^(A) to Y^(E) is —CF(—CH₂OH)—,each of X^(A) to X^(D) is —CF(—C(O)G)-; and when each of Y^(A) to Y^(E)is —CR^(A)R^(B)—, each of X^(A) to X^(D) is —CR^(A)R^(B)—; each of R^(A)and R^(B) is independently a fluorine atom, a C₁₋₁₆ perfluoroalkyl groupor a C₁₋₁₆ perfluoroalkyl group containing an etheric oxygen atom; G isa halogen atom or a C₁₋₁₀ alkoxy group; W^(A) and W^(B): each of them isindependently a fluorine atom, a C₁₋₁₆ perfluoroalkyl group or a C₁₋₁₆perfluoroalkyl group containing an etheric oxygen atom; and n: 0, 1 or2.